Search Results (10)

Cellulose tosylate (MCC-Tos) is a key derivative for surface modification and a crucial precursor for cellulose compatibilization in click reactions, enabling its functionalization for advanced applications. Replacing tosyl groups with alkyne groups broadens cellulose’s potential in biocompatible reactions, such as thiol-yne click chemistry and protein/enzyme immobilization. To achieve this, we optimized the heterogeneous synthesis of MCC-Tos using a Doehlert matrix statistical design, evaluating the influence and interaction of the reaction conditions. The optimized conditions—144 h reaction time, 10:1 molar ratio, and 30 °C—yielded a degree of substitution for tosyl groups (DS_tos) of 1.80, determined via elemental analysis and FTIR-ATR spectroscopy. The reaction kinetics followed a first-order model. A subsequent reaction with propargylamine produced aminopropargyl cellulose (MCC-P_NH), reducing DS_tos by 65%, which was confirmed via FTIR, and improving thermal stability by a margin of 30 °C (TGA/DTG). ¹³C CP/MAS NMR confirmed the alkyne group attachment, further validated via coupling an azide-functionalized coumarin through copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC). Fluorescence microscopy and UV spectroscopy were used to estimate a substitution degree of 0.21. This study establishes a feasible route for synthesizing alkyne-functionalized cellulose, paving the way for eco-friendly materials, including protein/enzyme bioconjugates, composites, and advanced materials via thiol-yne and CuAAC reactions. Full article

In recent years, polyelectrolytes have been successfully used as an alternative to non-collagenous proteins to promote interfibrillar biomineralization, to reproduce the spatial intercalation of mineral phases among collagen fibrils, and to design bioinspired scaffolds for hard tissue regeneration. Herein, hybrid nanofibers were fabricated via electrospinning, by using a mixture of Poly ɛ-caprolactone (PCL) and cationic cellulose derivatives, i.e., cellulose-bearing imidazolium tosylate (CIMD). The obtained fibers were self-assembled with Sodium Alginate (SA) by polyelectrolyte interactions with CIMD onto the fiber surface and, then, treated with simulated body fluid (SBF) to promote the precipitation of calcium phosphate (CaP) deposits. FTIR analysis confirmed the presence of SA and CaP, while SEM equipped with EDX analysis mapped the calcium phosphate constituent elements, estimating an average Ca/P ratio of about 1.33—falling in the range of biological apatites. Moreover, in vitro studies have confirmed the good response of mesenchymal cells (hMSCs) on biomineralized samples, since day 3, with a significant improvement in the presence of SA, due to the interaction of SA with CaP deposits. More interestingly, after a decay of metabolic activity on day 7, a relevant increase in cell proliferation can be recognized, in agreement with the beginning of the differentiation phase, confirmed by ALP results. Antibacterial tests performed by using different bacteria populations confirmed that nanofibers with an SA-CIMD complex show an optimal inhibitory response against S. mutans, S. aureus, and E. coli, with no significant decay due to the effect of CaP, in comparison with non-biomineralized controls. All these data suggest a promising use of these biomineralized fibers as bioinspired membranes with efficient antimicrobial and osteoconductive cues suitable to support bone healing/regeneration. Full article

Replacing petroleum-based polymers with biopolymers such as polysaccharides is essential for protecting our environment by saving fossil resources. A research field that can benefit from the application of more sustainable and renewable materials is photochemistry. Therefore, cellulose-based photoresists that could be photocrosslinked via UV irradiation (λ = 254 nm and λ = 365 nm) were developed. These biogenic polymers enable the manufacturing of sustainable coatings, even with imprinted microstructures, and cellulose-based bulk materials. Thus, herein, cellulose was functionalized with organic compounds containing carbon double bonds to introduce photocrosslinkable side groups directly onto the cellulose backbone. Therefore, unsaturated anhydrides such as methacrylic acid anhydride and unsaturated and polyunsaturated carboxylic acids such as linoleic acid were utilized. Additionally, these cellulose derivatives were modified with acetate or tosylate groups to generate cellulose-based polymers, which are soluble in organic solvents, making them suitable for multiple processing methods, such as casting, printing and coating. The photocurable resist was basically composed of the UV-crosslinkable biopolymer, an appropriate solvent and, if necessary, a photoinitiator. Moreover, these bio-based photoresists were UV-crosslinkable in the liquid and solid states after the removal of the solvent. Further, the manufactured cellulose-based architectures, even the bulk structures, could be entirely regenerated into pure cellulose devices via a sodium methoxide treatment. Full article

The use of polyelectrolytes is emerging as a fascinating strategy for the functionalization of biomedical membranes, due to their ability to enhance biological responses using the interaction effect of charged groups on multiple interface properties. Herein, two different polyelectrolytes were used to improve the antibacterial properties of polycaprolactone (PCL) nanofibers fabricated via electrospinning. First, a new cationic cellulose derivative, cellulose-bearing imidazolium tosylate (CIMD), was prepared via the nucleophilic substitution of the tosyl group using 1-methylimidazole, as confirmed by NMR analyses, and loaded into the PCL nanofibers. Secondly, sodium alginate (SA) was used to uniformly coat the fibers’ surface via self-assembly, as remarked through SEM-EDX analyses. Polyelectrolyte interactions between the CIMD and the SA, initially detected using a FTIR analysis, were confirmed via Z potential measurements: the formation of a CMID/SA complex promoted a substantial charge neutralization of the fibers’ surfaces with effects on the physical properties of the membrane in terms of water adsorption and in vitro degradation. Moreover, the presence of SA contributed to the in vitro response of human mesenchymal stem cells (hMSCs), as confirmed by a significant increase in the cells’ viability after 7 days in the case of the PCL/CMID/SA complex with respect to the PCL and PCL/CMID membranes. Contrariwise, SA did not nullify the antibacterial effect of CMID, as confirmed by the comparable resistance exhibited by S. mutans, S. aureus, and E. coli to the PCL/CIMD and PCL/CIMD/SA membranes. All the reported results corroborate the idea that the CIMD/SA functionalization of PCL nanofibers has a great potential for the fabrication of efficient antimicrobial membranes for wound healing. Full article

In biomedical applications, bacterial cellulose (BC) is widely used because of its cytocompatibility, high mechanical properties, and ultrafine nanofibrillar structure. However, biomedical use of neat BC is often limited due to its lack of antimicrobial properties. In the current article, we proposed a novel technique for preparing cationic BC hydrogel through in situ incorporation of cationic water-soluble cellulose derivative, cellulose bearing imidazolium tosylate function group (Cell-IMD), in the media used for BC preparation. Different concentrations of cationic cellulose derivative (2, 4, and 6%) were embedded into a highly inter-twined BC nanofibrillar network through the in situ biosynthesis until forming cationic cellulose gels. Cationic functionalization was deeply examined by the Fourier transform infrared (FT–IR), NMR spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD) methods. In vitro studies with L929 cells confirmed a good cytocompatibility of BC/cationic cellulose derivatives, and a significant increase in cell proliferation after 7 days, in the case of BC/Cell-IMD3 groups. Finally, antimicrobial assessment against Staphylococcus aureus, Streptococcus mutans, and Candida albicans was assessed, recording a good sensitivity in the case of the higher concentration of the cationic cellulose derivative. All the results suggest a promising use of cationic hybrid materials for biomedical and bio-sustainable applications (i.e., food packaging). Full article

Alpha- and beta-linked 1,3-glucans have been subjected to conversion with p-toluenesulfonic acid (tosyl) chloride and triethylamine under homogeneous reaction conditions in N,N-dimethyl acetamide/LiCl. Samples with a degree of substitution of tosyl groups (DS_Ts) of up to 1.91 were prepared by applying 5 mol reagent per mole repeating unit. Hence, the reactivity of α-1,3-glucan is comparable with cellulose and starch, while the β-1,3-linked glucan curdlan is less reactive. The samples dissolve in aprotic dipolar media independent of the DS_Ts and possess a solubility in less polar solvents that depends on the DS_Ts. NMR studies on the tosyl glucans and of the peracylated derivatives showed a preferred tosylation of position 2 of the repeating unit. However, the selectivity is less pronounced compared with starch. It could be concluded that the α-configurated glycosidic bond directs tosyl groups towards position 2. Full article

Cellulose based materials are emerging in the commercial fields and high-end applications, especially in biomedicines. Aminated cellulose derivatives have been extensively used for various applications but limited data are available regarding its cytotoxicity studies for biomedical application. The aim of this study is to synthesize different 6-deoxy-amino-cellulose derivatives from Microcrystalline cellulose (MCC) via tosylation and explore their cytotoxic potential against normal fibroblasts, melanoma and breast cancer. 6-deoxy-6-hydrazide Cellulose (Cell Hyd) 6-deoxy-6-diethylamide Cellulose (Cell DEA) and 6-deoxy-6-diethyltriamine Cellulose (Cell DETA) were prepared and characterized by various technologies like Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR), nuclear magnetic resonance spectroscopy (NMR), X-ray diffractogram (XRD), Scanning Electron microscopy (SEM), Elemental Analysis and Zeta potential measurements. Cytotoxicity was evaluated against normal fibroblasts (NIH3T3), mouse skin melanoma (B16F10), human epithelial adenocarcinoma (MDA-MB-231) and human breast adenocarcinoma (MCF-7) cell lines. IC₅₀ values obtained from cytotoxicity assay and live/dead assay images analysis showed MCC was non cytotoxic while Cell Hyd, Cell DEA and Cell DETA exhibited noncytotoxic activity up to 200 μg/mL to normal fibroblast cells NIH3T3, suggesting its safe use in medical fields. The mouse skin melanoma (B16F10) are the most sensitive cells to the cytotoxic effects of Cell Hyd, Cell DEA and Cell DETA, followed by human breast adenocarcinoma (MCF-7). Based on our study, it is suggested that aminated cellulose derivatives could be promising candidates for tissue engineering applications and in cancer inhibiting studies in future. Full article

While intensive efforts are made to prepare carbon fiber reinforced plastics from renewable sources, less emphasis is directed towards elaborating green approaches for carbon fiber surface modification to improve the interfacial adhesion in these composites. In this study, we covalently attach lignin, a renewable feedstock, to a graphitic surface for the first time. The covalent bond is established via aromatic anchoring groups with amine functions taking part in a nucleophilic displacement reaction with a tosylated lignin derivative. The successful grafting procedures were confirmed by cyclic voltammetry, X-ray photoelectron spectroscopy, and field emission scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. Both fragmentation and microdroplet tests were conducted to evaluate the interfacial shear strength of lignin coated carbon fiber samples embedded in a green cellulose propionate matrix and in a commercially used epoxy resin. The microdroplet test showed ~27% and ~65% increases in interfacial shear strength for the epoxy and cellulose propionate matrix, respectively. For the epoxy matrix covalent bond, it is expected to form with lignin, while for the cellulosic matrix hydrogen bond formation might take place; furthermore, plastisizing effects are also considered. Our study opens the gates for utilizing lignin coating to improve the shear tolerance of innovative composites. Full article

Chiral epoxides—such as ethyl and methyl (S)-3-(oxiran-2-yl)propanoates ((S)-1a/1b)—are valuable precursors in many chemical syntheses. Until recently, these compounds were synthesized from glutamic acid in four steps (deamination, reduction, tosylation and epoxide formation) in low to moderate overall yield (20%–50%). Moreover, this procedure requires some harmful reagents such as sodium nitrite ((eco)toxic) and borane (carcinogen). Herein, starting from levoglucosenone (LGO), a biobased chiral compound obtained through the flash pyrolysis of acidified cellulose, we propose a safer and more sustainable chemo-enzymatic synthetic pathway involving lipase-mediated Baeyer-Villiger oxidation, palladium-catalyzed hydrogenation, tosylation and treatment with sodium ethoxide/methoxide as key steps. This route afforded ethyl and methyl (S)-3-(oxiran-2-yl)propanoates in 57% overall yield, respectively. To demonstrate the potentiality of this new synthetic pathway from LGO, the synthesis of high value-added (S)-dairy lactone was undertaken from these epoxides and provided the target in 37% overall yield from LGO. Full article

The main objective of this work is the grafting of polycaprolactone diol (PCL) on the surface of oxidized nanocelluloses (ONC) in order to enhance the compatibility between the hydrophilic cellulose nanofibres and the hydrophobic polymer matrix. This grafting was successfully realized with a new strategy known as click chemistry. In this context, the oxidized nanocelluloses bearing alkyl groups (ONC-PR) were prepared by reacting amino groups of propargylamine (PR) with carboxyl groups of ONC. In parallel, PCL was converted into azido-polycaprolactone (PCL-N₃) in two steps: (i) tosylation of polycaprolactone (PCL-OTs) and (ii) conversion of PCL-OTs into PCL-N₃ by nucleophilic displacement using sodium azide. Finally, ONC-PR was reacted with PCL-N₃ in heterogeneous conditions through click chemistry in order to prepare polycaprolactone grafted oxidized nanocellulose (ONC-g-PCL), which could be suitable for improving the interfacial adhesion in the composite materials. The grafted samples were characterized by transmission electron microscopy and by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and Carbon-13 nuclear magnetic resonance spectroscopy (¹³C-NMR) spectroscopic techniques. Full article